US9353223B2 - Polyamic acid, polyimide, polyamic acid solution, and use of polyimide - Google Patents

Polyamic acid, polyimide, polyamic acid solution, and use of polyimide Download PDF

Info

Publication number
US9353223B2
US9353223B2 US14/409,126 US201314409126A US9353223B2 US 9353223 B2 US9353223 B2 US 9353223B2 US 201314409126 A US201314409126 A US 201314409126A US 9353223 B2 US9353223 B2 US 9353223B2
Authority
US
United States
Prior art keywords
formula
unit represented
constitutional unit
polyimide
polyamic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US14/409,126
Other languages
English (en)
Other versions
US20150183931A1 (en
Inventor
Mari Fujii
Shinji Ozawa
Tomohiro Abo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kaneka Corp
Original Assignee
Kaneka Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kaneka Corp filed Critical Kaneka Corp
Assigned to KANEKA CORPORATION reassignment KANEKA CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ABO, Tomohiro, FUJII, MARI, OZAWA, SHINJI
Publication of US20150183931A1 publication Critical patent/US20150183931A1/en
Application granted granted Critical
Publication of US9353223B2 publication Critical patent/US9353223B2/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements

Definitions

  • the present invention relates to a polyamic acid, a polyimide, and a polyamic acid solution.
  • the present invention further relates to an electronic device material, a TFT substrate, a flexible display substrate, a color filter, a printed matter, an optical material, a liquid crystal display device, an image display device such as an organic EL and an electronic paper, a 3-D display, a solar cell, a touch panel, a transparent conductive film substrate, and an alternative material for a part which has conventionally been made of glass, each of which are made with the use of a polyimide.
  • the plastic film substrate is required to have heat resistance sufficient for being applied to the high temperature process.
  • the film on which the inorganic devices have been provided may be curved and further the inorganic devices may be broken, due to a difference in linear thermal expansion coefficient between the film and the inorganic materials. Therefore, a material has been demanded which has (i) heat resistance and (ii) a linear thermal expansion coefficient equivalent to that of the inorganic material.
  • the plastic film substrate In a case where light from a display element (such as liquid crystal or organic EL) is emitted through a plastic film substrate (e.g., in a case of a bottom emission type organic EL), the plastic film substrate needs to have transparency. In particular, the plastic film substrate is requested to have a high optical transmittance in a visible light range, i.e., in a wavelength range of 400 nm or less. In a case where light passes through a retardation film and/or a polarizing plate (e.g., in a case of a liquid crystal display or a touch panel), the plastic film substrate is required to have high optical isotropy, in addition to transparency.
  • a display element such as liquid crystal or organic EL
  • Processes for producing such devices are classified into a batch type and a roll-to-roll type.
  • the roll-to-roll production process it is necessary to prepare new equipment, and also necessary to overcome some problems caused due to rotation and contact.
  • a coating resin solution which has been applied to a glass substrate, is dried so as to be formed into a substrate, and then the substrate thus obtained is peeled off.
  • conventional equipment for processing a glass substrate such as a TFT can be used, and is therefore advantageous in terms of cost.
  • a polyimide material As a material which satisfies the above described requests, a polyimide material has been studied which is known as a material having excellent heat resistance.
  • a monomer having a rigid structure and an alicyclic monomer are generally used (see Patent Literature 1 and Patent Literature 2).
  • Patent Literature 3 it is known that a polyimide having a fluorene structure shows heat resistance and a low water-absorbing property (Patent Literature 3).
  • Patent Literature 1 is excellent in heat resistance and low thermal expansion property but does not have sufficient transparency, and Patent Literature 1 is silent about birefringence.
  • the polyimide disclosed in Patent Literature 2 is excellent in transparency and low thermal expansion characteristic but Patent Literature 2 is silent about birefringence.
  • the polyimide containing a fluorene structure disclosed in Patent Literature 3 is excellent in heat resistance and low thermal expansion property but does not have sufficient transparency, and Patent Literature 3 is silent about birefringence.
  • the present invention is accomplished in view of the actual circumstances, and its object is to obtain (i) a polyimide which is excellent in heat resistance, low thermal expansion property, and transparency and shows low birefringence, and (ii) a polyamic acid as a precursor of the polyimide. Further, an object of the present invention is to provide, with the use of the polyimide and the polyamic acid, a product or a member which is highly requested to have heat resistance and transparency. In particular, an object of the present invention is to provide a product and a member in which the polyimide and the polyamic acid of the present invention are provided on a surface of an inorganic substance such as glass, metal, a metal oxide, and single crystal silicon.
  • the inventors of the present invention have found it effective to introduce a rigid structure and an alicyclic structure in a skeleton and to use also a monomer having a fluorene skeleton, in order to attain the object, i.e., to obtain the polyimide that is excellent in heat resistance, low thermal expansion property, and transparency and shows low birefringence,
  • a polyamic acid of the present invention contains a constitutional unit represented by General Formula (1) and a constitutional unit represented by General Formula (2):
  • each of “R 1 ” and “R 2 ” is a group selected from a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, and an alkoxyl group, “R 1 ” and “R 2 ” are identical with each other or different from each other, and “A” in General Formula (2) is an acid dianhydride-derived component which is one selected from a constitutional unit represented by Formula (3), a constitutional unit represented by Formula (4), and a constitutional unit represented by Formula (5):
  • a polyimide of the present invention contains a constitutional unit represented by General Formula (6) and a constitutional unit represented by General Formula (7):
  • each of “R1” and “R2” is a group selected from a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, and an alkoxyl group
  • “R1” and “R2” are identical with each other or different from each other
  • “A” in General Formula (7) is an acid dianhydride-derived component which is one selected from a constitutional unit represented by Formula (3), a constitutional unit represented by Formula (4), and a constitutional unit represented by Formula (5):
  • the polyimide of the present invention and the polyimide prepared with the use of the polyamic acid of the present invention have low birefringence, in addition to heat resistance, low thermal expansion property, and transparency. Therefore, the polyimide of the present invention and the polyamic acid of the present invention are suitable for a film or a coating for a member that is required to have low birefringence, in addition to heat resistance, low thermal expansion property, and transparency.
  • FIG. 1 is a view schematically illustrating a state in which detachment or floating occurs between a polyimide and a support when a polyamic acid solution applied to the support is imidized.
  • the polyamic acid prepared in the present invention contains a constitutional unit represented by General Formula (1) and a constitutional unit represented by General Formula (2):
  • each of “R 1 ” and “R 2 ” is a group selected from a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, and an alkoxyl group, and “R 1 ” and “R 2 ” can be identical with each other or different from each other.
  • “R 1 ” and “R 2 ” are independently the hydrogen atom or the alkyl group, and in view of heat resistance, each of “R 1 ” and “R 2 ” is particularly preferably the hydrogen atom.
  • the constitutional unit represented by Formula (1) is most preferably a polyamic acid constitutional unit which is represented by Formula (8) and is obtained from 3,3′,4,4′-biphenyltetracarboxylic dianhydride and 1,4-cyclohexanediamine.
  • “A” in General Formula (2) is a constitutional unit containing a fluorene skeleton.
  • “A” is preferably one selected from a constitutional unit represented by Formula (3), a constitutional unit represented by Formula (4), and a constitutional unit represented by Formula (5).
  • “A” is particularly preferably the constitutional unit represented by Formula (3).
  • the constitutional unit represented by Formula (2) is preferably one selected from the constitutional unit represented by Formula (9), the constitutional unit represented by Formula (12), and the constitutional unit represented by Formula (13).
  • the constitutional unit represented by Formula (2) is most preferably the constitutional unit represented by Formula (9).
  • a total number of moles of the constitutional unit represented by General Formula (1) and the constitutional unit represented by General Formula (2) in the polyamic acid relative to the number of moles of the polyamic acid is preferably 70% or higher, more preferably 80% or higher, particularly preferably 90% or higher.
  • the number of moles of polyamic acid indicates the number of moles of all diamine-derived constitutional units constituting the polyamic acid or the number of moles of all acid dianhydride-derived constitutional units constituting the polyamic acid.
  • the polyamic acid of the present invention contains the constitutional unit represented by General Formula (1) and the constitutional unit represented by General Formula (2).
  • a molar ratio expressed by the number of moles of the constitutional unit represented by Formula (1)/the number of moles of the constitutional unit represented by Formula (2) is preferably 30/70 or higher, more preferably 50/50 or higher, in view of expression of low thermal expansion property.
  • the molar ratio expressed by the number of moles of the constitutional unit represented by Formula (1)/the number of moles of the constitutional unit represented by Formula (2) is preferably 99/1 or lower, more preferably 98/2 or lower, further preferably 97/3 or lower, particularly preferably 95/5 or lower, most preferably 80/20 or lower.
  • the polyamic acid of the present invention contains the constitutional unit represented by General Formula (1) and the constitutional unit represented by General Formula (2).
  • the constitutional unit represented by General Formula (1) is the constitutional unit represented by Formula (8)
  • the constitutional unit represented by General Formula (2) is the constitutional unit represented by Formula (9).
  • a molar ratio expressed by the number of moles of the constitutional unit represented by Formula (8)/the number of moles of the constitutional unit represented by Formula (9) is preferably 30/70 or higher, more preferably 50/50 or higher, in view of expression of low thermal expansion property.
  • the molar ratio expressed by the number of moles of the constitutional unit represented by Formula (8)/the number of moles of the constitutional unit represented by Formula (9) is preferably 99/1 or lower, more preferably 98/2 or lower, further preferably 97/3 or lower, particularly preferably 95/5 or lower, most preferably 80/20 or lower.
  • a batch type process for producing a device i.e., a process in which (i) a polyamic acid solution, which has been applied to a support such as glass, is imidized by heating so as to be formed into a substrate on which electron elements and the like are provided and then (ii) the substrate thus obtained is peeled off, it is more preferable that sufficient adhesiveness is secured between the support and the polyimide.
  • adhesiveness does not mean adhesion strength but rather means a degree of detachment or floating between the polyimide and the support when the polyamic acid solution applied to the support such as glass is imidized.
  • FIG. 1 is a view schematically illustrating a state in which detachment or floating occurs between a polyimide and a support 1 (e.g., glass) when a polyamic acid solution 2 applied to the support 1 is imidized by heating.
  • a support 1 e.g., glass
  • the water and/or organic solvent remaining between the support and the polyamic acid that is being imidized forms bubble-like detachment or floating between the obtained polyimide and the support as illustrated in (c) of FIG. 1 .
  • the water and/or organic solvent is discharged from the bubble-like detachment or floating through the polyimide or the support, and then the bubble part of detachment or floating ultimately becomes a space filled with air.
  • the molar ratio expressed by the number of moles of the constitutional unit represented by Formula (1)/the number of moles of the constitutional unit represented by Formula (2) more preferably the molar ratio expressed by the number of moles of the constitutional unit represented by Formula (8)/the number of moles of the constitutional unit represented by Formula (9) is 99/1 or lower, adhesiveness between the support and the polyimide is improved.
  • the molar ratio expressed by the number of moles of the constitutional unit represented by Formula (1)/the number of moles of the constitutional unit represented by Formula (2) more preferably the molar ratio expressed by the number of moles of the constitutional unit represented by Formula (8)/the number of moles of the constitutional unit represented by Formula (9) is 99/1 or lower, it is possible to achieve low birefringence and good adhesiveness between the support and the polyimide when the polyamic acid solution applied to the support is imidized.
  • the number of moles of the constitutional unit represented by Formula (2)/(the number of moles of the constitutional unit represented by Formula (1)+the number of moles of the constitutional unit represented by Formula (2)) is more preferably 0.01 or more and less than 0.05, further preferably 0.02 or more and less than 0.05.
  • the number of moles of the constitutional unit represented by Formula (9)/(the number of moles of the constitutional unit represented by Formula (8)+the number of moles of the constitutional unit represented by Formula (9)) is more preferably 0.01 or more and less than 0.05, further preferably 0.02 or more and less than 0.05.
  • the polyimide prepared in the present invention contains the constitutional unit represented by General Formula (6) and the constitutional unit represented by General Formula (7):
  • General Formulae (6) and (7) are synonymous with respective “R 1 ”, “R 2 ”, and “A” in General Formula (1) and General Formula (2). That is, General Formula (6) is most preferably a polyimide constitutional unit which is obtained from 3,3′,4,4′-biphenyltetracarboxylic dianhydride and 1,4-cyclohexanediamine as indicated in Formula (10).
  • “A” is a constitutional unit containing a fluorene skeleton, and is preferably one selected from constitutional units represented by Formulae (3), (4), and (5) in view of low birefringence, and is particularly preferably the constitutional unit represented by Formula (3) in view of heat resistance. That is, the constitutional unit represented by General Formula (7) is preferably one selected from a constitutional unit represented by Formula (11), a constitutional unit represented by Formula (14), and a constitutional unit represented by Formula (15), and is most preferably the constitutional unit represented by Formula (11) in view of heat resistance.
  • the total number of moles of the constitutional unit represented by General Formula (6) and the constitutional unit represented by General Formula (7) is preferably 70% or higher, more preferably 80% or higher, particularly preferably 90% or higher, relative to the number of moles of the polyimide.
  • the number of moles of the polyimide indicates the number of moles of all diamine-derived units constituting the polyimide or the number of moles of all acid dianhydride-derived units constituting the polyimide.
  • the polyimide of the present invention contains the constitutional unit represented by General Formula (6) and the constitutional unit represented by General Formula (7).
  • a molar ratio expressed by the number of moles of the constitutional unit represented by Formula (6)/the number of moles of the constitutional unit represented by Formula (7) is preferably 30/70 or higher, more preferably 50/50 or higher, in view of expression of low thermal expansion property.
  • the molar ratio expressed by the number of moles of the constitutional unit represented by Formula (6)/the number of moles of the constitutional unit represented by Formula (7) is preferably 99/1 or lower, more preferably 98/2 or lower, further preferably 97/3 or lower, particularly preferably 95/5 or lower, most preferably 80/20 or lower.
  • the polyimide of the present invention contains the constitutional unit represented by General Formula (6) and the constitutional unit represented by General Formula (7).
  • the constitutional unit represented by General Formula (6) is the constitutional unit represented by Formula (10)
  • the constitutional unit represented by General Formula (7) is the constitutional unit represented by Formula (11).
  • a molar ratio expressed by the number of moles of the constitutional unit represented by Formula (10)/the number of moles of the constitutional unit represented by Formula (11) is preferably 30/70 or higher, more preferably 50/50 or higher, in view of expression of low thermal expansion property.
  • the molar ratio expressed by the number of moles of the constitutional unit represented by Formula (10)/the number of moles of the constitutional unit represented by Formula (11) is preferably 99/1 or lower, more preferably 98/2 or lower, further preferably 97/3 or lower, particularly preferably 95/5 or lower, most preferably 80/20 or lower.
  • the number of moles of the constitutional unit represented by Formula (7)/(the number of moles of the constitutional unit represented by Formula (6)+the number of moles of the constitutional unit represented by Formula (7)) is more preferably 0.01 or more and less than 0.05, further preferably 0.02 or more and less than 0.05.
  • the number of moles of the constitutional unit represented by Formula (11)/(the number of moles of the constitutional unit represented by Formula (10)+the number of moles of the constitutional unit represented by Formula (11)) is more preferably 0.01 or more and less than 0.05, further preferably 0.02 or more and less than 0.05.
  • the polyimide of the present invention can be obtained by imidizing the polyamic acid that contains the constitutional unit represented by General Formula (1) and the constitutional unit represented by General Formula (2).
  • the polyimide of the present invention can be synthesized from a generally known precursor such as polyamic acid ester or can be produced without using a precursor.
  • the polyamic acid of the present invention can be synthesized by a generally known method, and can be obtained by causing a diamine to be reacted with tetracarboxylic dianhydride in an organic solvent.
  • a diamine solution is prepared by dissolving a diamine in an organic solvent or by dispersing the diamine in an organic solvent in a slurry form in an inert atmosphere such as argon or nitrogen.
  • tetracarboxylic dianhydride which (i) has been dissolved in an organic solvent or dispersed in an organic solvent in a slurry form or (ii) is in a solid form, is added to the diamine solution.
  • a polyamic acid copolymer can be arbitrarily obtained by adjusting the number of total moles of one or more diamine components to be substantially equal to the number of total moles of one or more tetracarboxylic dianhydride components.
  • a temperature condition in the reaction of the diamine and the tetracarboxylic dianhydride, that is, in the synthetic reaction of the polyamic acid is not limited to a particular one.
  • the temperature in the synthetic reaction of the polyamic acid can be set to a range between 50° C. and 150° C. as appropriate.
  • the temperature in the synthetic reaction of the polyamic acid is preferably set to 80° C. or lower, more preferably 0° C. or higher and 50° C. or lower, in order to inhibit decrease in molecular weight of the polyamic acid.
  • a reaction time can be arbitrarily set within a range between 10 minutes and 30 hours.
  • the organic solvent used in the synthetic reaction of the polyamic acid is not limited to a particular one, provided that the solvent is an organic polar solvent.
  • the reaction of the diamine and the tetracarboxylic dianhydride progresses, the polyamic acid is generated, and viscosity of a reaction liquid is increased.
  • the organic solvent used in polymerization of a polyamic acid is preferably a solvent which can (i) dissolve a tetracarboxylic dianhydride and a diamine to be used and further (ii) dissolve a generated polyamic acid.
  • organic solvent used in the synthetic reaction of polyamic acid encompass urea solvents such as tetramethylurea and N,N-dimethylethylurea; sulfoxide or sulphone solvents such as dimethyl sulfoxide, diphenyl sulfone, and tetramethyl sulfone; ester solvents such as N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF), N,N′-diethylacetamide, N-methyl-2-pyrolidone (NMP), and ⁇ -butyrolactone; amide solvents such as hexamethylphosphoric triamide; alkyl halide solvents such as chloroform and methylene chloride; aromatic hydrocarbon solvents such as benzene and toluene; phenol solvents such as phenol and cresol; ketone solvents such as cyclopentanone; and ether solvents such as tetrahydrofuran, 1,3
  • the organic solvent used in the synthetic reaction of the polyamic acid is preferably selected from the amide solvent, the ketone solvent, the ester solvent, and the ether solvent, particularly preferably the amide solvent such as DMF, DMAC, or NMP.
  • the polyimide of the present invention can be obtained by a known method, and is not limited to a particular production method.
  • the polyimide of the present invention is preferably obtained from a polyamic acid which is a precursor thereof.
  • a method is described in which a polyamic acid is imidized in order to obtain a polyimide with the use of the polyamic acid.
  • the imidization is carried out by cyclodehydration of the polyamic acid.
  • the cyclodehydration can be carried out with an azeotropic method using an azeotropic solvent, a thermal method, or a chemical method.
  • the imidization from the polyamic acid to the polyimide can be carried out with any ratio between 1% and 100%. That is, it is possible to synthesize a polyamic acid which is partially imidized.
  • a solution containing a polyamic acid and an organic solvent is meant to be a polyamic acid solution.
  • the organic solvent contained in the polyamic acid solution can be an organic solvent similar to that used in the synthetic reaction of the polyamic acid.
  • the organic solvent is more preferably one selected from the amide solvent, the ketone solvent, the ester solvent, and the ether solvent, particularly preferably the amide solvent such as DMF, DMAC, or NMP.
  • a reaction solution itself thus synthesized is sometimes referred to as “polyamic acid solution”.
  • the cyclodehydration can be carried out by heating the polyamic acid.
  • a method for heating the polyamic acid is not limited to a particular one, and can be, for example, a method in which the polyamic acid solution is flow-casted or applied to a support such as a glass plate, a metal plate, or PET (polyethylene terephthalate), and then heat treatment is carried out at a temperature within a range between 80° C. and 500° C.
  • the cyclodehydration of the polyamic acid can be carried out as follows: that is, the polyamic acid solution is directly put into a container which has been subjected to a release treatment such as coating with a fluorocarbon resin, and the polyamic acid solution is dried with heat under reduced pressure.
  • the polyimide can be obtained by thus carrying out the cyclodehydration of the polyamic acid.
  • the heating time of each process varies depending on a throughput and a heating temperature of the polyamic acid solution subjected to the cyclodehydration. In general, it is preferable that heating is carried out for a time within a range between 1 minute and 5 hours from when a process temperature reaches a maximum temperature.
  • a polyamic acid solution to which an imidizing agent and/or a dehydrating catalyst have(has) been added can be imidized by heating with the method as above described.
  • the imidizing agent is not limited to a particular one and can be tertiary amine.
  • the tertiary amine is further preferably heterocyclic tertiary amine.
  • Concrete examples of the heterocyclic tertiary amine preferably encompass pyridine, picoline, quinoline, and isoquinoline.
  • Concrete examples of the dehydrating catalyst preferably encompass acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride.
  • an added amount of the imidizing agent is preferably 0.5 to 5.0 molar equivalent, more preferably 0.7 to 2.5 molar equivalent, particularly preferably 0.8 to 2.0 molar equivalent, relative to an amide group of the polyamic acid.
  • an added amount of the dehydrating catalyst is preferably 0.5 to 10.0 molar equivalent, more preferably 0.7 to 5.0 molar equivalent, particularly preferably 0.8 to 3.0 molar equivalent, relative to the amide group of the polyamic acid.
  • the imidizing agent and/or the dehydrating catalyst can be added directly without being dissolved in an organic solvent or can be dissolved in an organic solvent and then added. According to the method in which the imidizing agent and/or the dehydrating catalyst are/is directly added without being dissolved in an organic solvent, a reaction rapidly progresses before the imidizing agent and/or the dehydrating catalyst are/is diffused, and therefore gel may be generated. Under the circumstances, it is more preferable to mix a solution, which has been obtained by dissolving the imidizing agent and/or the dehydrating catalyst in an organic solvent, with the polyamic acid solution.
  • a weight-average molecular weight of the polyamic acid and the polyimide of the present invention is preferably within a range of 10,000 or more and 500,000 or less, more preferably within a range between 20,000 and 300,000, further preferably within a range between 30,000 and 200,000.
  • the weight-average molecular weight is 10,000 or more, the polyamic acid and the polyimide can be formed into a coating or a film.
  • the weight-average molecular weight is 500,000 or less
  • the polyamic acid and the polyimide show sufficient solubility with respect to a solvent, and it is therefore possible to obtain, from the polyamic acid solution (later described), a coating or a film which has a smooth surface and a uniform film thickness.
  • the molecular weight used herein is equivalent to a molecular weight of polyethylene glycol determined by gel permeation chromatography (GPC).
  • the polyimide of the present invention can be prepared by applying a polyamic acid solution to a support and then drying or heating the polyamic acid solution.
  • a film of the polyimide obtained in the method as above described is sometimes referred to as “polyimide film”.
  • the polyamic acid solution can be a solution which is partially imidized.
  • the drying or heating can be carried out in the presence of air or in a nitrogen atmosphere. In view of transparency, the drying or heating is particularly preferably carried out in the nitrogen atmosphere.
  • the support to which the polyamic acid solution is applied can be a glass substrate; a metal substrate or a metal belt such as SUS; or a plastic film such as polyethylene terephthalate, polycarbonate, polyacrylate, polyethylenenaphthalate, or triacetylcellulose. Note, however, that the support is not limited to these. For use in the current batch type process of producing a device, it is preferable to use a glass substrate.
  • a condition suitable for the process can be selected, and the drying temperature or the heating temperature is not limited to a particular one, provided that the characteristics are not influenced.
  • Transparency of the polyimide is expressed based on, for example, total-light transmittance or haze in accordance with JIS K7105-1981.
  • the total-light transmittance of the polyimide is preferably 80% or higher, more preferably 85% or higher.
  • the haze is preferably 2.0% or lower, more preferably 1.0% or lower.
  • the polyimide is demanded to have high transmittance in the entire wavelength range.
  • the polyimide tends to absorb light on a shorter wavelength side, and the film itself is often colored in yellow.
  • an optical transmittance at a wavelength of 400 nm of the polyimide which has a film thickness of 10 ⁇ m, is preferably 50% or higher, more preferably 60% or higher, further preferably higher than 70%.
  • the optical transmittance at the wavelength of 400 nm is measured with an ultraviolet-visible spectrophotometer.
  • the polyimide of the present invention has a low linear thermal expansion characteristic and dimensional stability through heating, as film characteristics.
  • the values are measured by thermomechanical analysis (TMA) as follows: That is, (i) TMA120C (manufactured by Seiko Instruments Inc.) is used (sample size: width of 3 mm and length of 10 mm, film thickness is measured and cross-sectional area of film is calculated), (ii) a load is set to 3 gf, (iii) a temperature is once heated up from 10° C. to 340° C. at 10° C./min, then cooled down to 10° C., and then heated up again to 340° C.
  • a linear thermal expansion coefficient in a temperature range from 100° C. to 300° C. is obtained from an amount of change in distortion of the sample per unit temperature range from 100° C. to 300° C. in the second heating-up.
  • the polyimide which has the linear thermal expansion coefficient, thus calculated of 50 ppm/K or less, more preferably 40 ppm/K or less.
  • a glass transition temperature is preferably as high as possible.
  • a glass transition temperature measured at a heating rate of 10° C./min is preferably 250° C. or higher, more preferably 300° C. or higher because it is possible to withstand even a high process temperature.
  • the polyimide preferably has an optical characteristic of low birefringence.
  • a polyimide is easily oriented in a plane, and has a large difference (birefringence) in refractive index between an in-plane direction and a thickness direction.
  • birefringence tends to be high.
  • nx ⁇ ny ⁇ 0.0010 and ( nx+ny )/2 ⁇ nz ⁇ 0.160 it is more preferable to satisfy the following: nx ⁇ ny ⁇ 0.0010 and ( nx+ny )/2 ⁇ nz ⁇ 0.120 it is further preferable to satisfy the following: nx ⁇ ny ⁇ 0.0010 and ( nx+ny )/2 ⁇ nz ⁇ 0.100 and, because higher optical isotropy is preferable, it is particularly preferable to satisfy the following: nx ⁇ ny ⁇ 0.0010 and ( nx+ny )/2 ⁇ nz ⁇ 0.050 where “nx” is a maximum in-plane refractive index, “ny” is a minimum in-plane refractive index, and “nz” is a refractive index in the thickness direction.
  • nx+ny/2 ⁇ nz indicates a difference in refractive index between the in-plane direction and the thickness direction, i.e., birefringence. This value is preferably as low as possible because further excellent optical isotropy can be achieved.
  • nx ⁇ ny is more preferably less than 0.0002, further preferably less than 0.0001.
  • the polyamic acid and the polyimide of the present invention can be used, as they are, in a coating process or a shaping process for producing a product or a member.
  • the polyamic acid and the polyimide of the present invention can be a laminate for carrying out a process of, for example, further coating an object that has been shaped in a film.
  • a polyamic acid composition and polyimide resin composition can be prepared by (i) dissolving or dispersing the polyamic acid and the polyimide in an organic solvent and further (ii) mixing with a photo-curing or thermosetting component, a non-polymerizable binder resin other than the polyamic acid and the polyimide of the present invention, and other components.
  • the polyamic acid and the polyimide can be mixed with other various organic or inorganic low-molecular or high-molecular compounds.
  • a dye for example, it is possible to use a dye, a surfactant, a leveling agent, an elasticizer, fine particles, a sensitizer, and the like.
  • the fine particles encompass, for example, (i) organic fine particles such as polystyrene and polytetrafluoroethylene and (ii) inorganic fine particles such as colloidal silica, carbon, and sheet silicate. Those fine particles can be porous or have a hollow structure.
  • the fine particles can serve as or can be in a form of a pigment, a filler, a fiber, and the like.
  • the polyamic acid represented by General Formulae (1) and (2) or the polyimide represented by Formulae (6) and (7) is generally contained within a range between 60% by weight and 99.9% by weight relative to an entire solid content of a composition.
  • the polyamic acid containing the constitutional unit represented by General Formula (1) and the constitutional unit represented by General Formula (2) or the polyimide containing the constitutional unit represented by General Formula (6) and the constitutional unit represented by General Formula (7) is generally contained within a range between 60% by weight and 99.9% by weight relative to the entire solid content of the composition.
  • the polyamic acid containing the constitutional unit represented by Formula (8) and the constitutional unit represented by Formula (9) or the polyimide containing the constitutional unit represented by General Formula (10) and the constitutional unit represented by General Formula (11) is generally contained within a range between 60% by weight and 99.9% by weight relative to the entire solid content of the composition.
  • “99.9% by weight” means “substantially all”.
  • a mixing ratio of other arbitrary component(s) is preferably within a range between 0.1% by weight and 95% by weight relative to an entire solid content of the polyimide. In a case where the mixing ratio is 0.1% by weight or higher, an effect of an additive can be easily brought about.
  • the mixing ratio is 95% by weight or lower, characteristics of the resin composition can be easily reflected in an end product.
  • the “solid content of the composition” indicates all components other than the organic solvent, and a liquid monomer component is also encompassed in the solid content.
  • the polyimide film of the present invention can have a surface on which various inorganic thin films (such as a metal oxide film and a transparent electrode film) are formed.
  • a method for preparing such inorganic thin films is not limited to a particular one and can be, for example, a CVD method and PVD methods such as a sputtering method, a vacuum vapor deposition method, and an ion plating method.
  • the polyimide of the present invention (i) has low birefringence, in addition to heat resistance, low thermal expansion property, and transparency and (ii) provides good adhesiveness between the support and the polyimide. Therefore, the polyimide of the present invention is preferably used in a field and a product for which the characteristics are effective. Examples of such a field and a product encompass a printed matter, a color filter, a flexible display, an optical film, a liquid crystal display device, an image display device such as an organic EL and an electronic paper, a 3-D display, a touch panel, a transparent conductive film substrate, and a solar cell. It is further preferable to use the polyimide of the present invention as an alternative material for a part which has conventionally been made of glass.
  • the substrate encompasses, for example, a TFT substrate, an ITO substrate, and a flexible display substrate.
  • the image display device encompasses, for example, an organic EL, an electronic paper, and a touch panel.
  • the optical material encompasses, for example, a color filter.
  • the polyimide of the present invention is expected to be used as an antireflection film, hologram, an optical member or a constructional material, and a structure.
  • the polyamic acid, the polyimide, and the polyamic acid solution of the present invention can be suitably used in a batch type device producing process in which (i) a polyamic acid solution is applied to a support and is then imidized by heating so as to form a substrate on which electron elements and the like are provided, and (ii) the substrate is then peeled off from the support. Therefore, the present invention includes a method for manufacturing an electronic device, which method includes the step of forming a substrate in which step (i) a polyamic acid solution is applied to a support and is then imidized by heating, and (ii) electron elements and the like are provided on the polyimide film thus formed on the support. Moreover, the method for manufacturing the electronic device can further include the step of peeling off the polyimide substrate, on which the electron elements and the like have been formed, from the support after the step of forming the substrate.
  • the present invention has the following configurations:
  • each of “R 1 ” and “R 2 ” is a group selected from a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, and an alkoxyl group, “R 1 ” and “R 2 ” are identical with each other or different from each other, and “A” in General Formula (2) is an acid dianhydride-derived component which is one selected from a constitutional unit represented by Formula (3), a constitutional unit represented by Formula (4), and a constitutional unit represented by Formula (5):
  • each of “R1” and “R2” is a group selected from a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, and an alkoxyl group
  • “R1” and “R2” are identical with each other or different from each other
  • “A” in General Formula (7) is an acid dianhydride-derived component which is one selected from a constitutional unit represented by Formula (3), a constitutional unit represented by Formula (4), and a constitutional unit represented by Formula (5):
  • nx ⁇ ny ⁇ 0.0010 and (nx+ny)/2 ⁇ nz ⁇ 0.160 are satisfied, where “nx” is a maximum in-plane refractive index, “ny” is a minimum in-plane refractive index, and “nz” is a refractive index in a thickness direction.
  • Mw weight-average molecular weight
  • Optical transmittance of a polyimide film at a wavelength ranging from 200 nm to 800 nm was measured with the use of an ultraviolet-visible-near infrared spectrophotometer (V-650, manufactured by JASCO Corporation), and optical transmittance at a wavelength of 400 nm was used as an indicator. Moreover, a wavelength (cutoff wavelength) at which transmittance is 0.5% or lower was also obtained.
  • V-650 ultraviolet-visible-near infrared spectrophotometer
  • a linear thermal expansion coefficient was measured with the use of TMA120C (manufactured by Seiko Instruments Inc.) (sample size: width of 3 mm, length of 10 mm; film thickness was measured and cross-sectional area of film was calculated).
  • a load was set to 3 gf, and a temperature was once heated up from 10° C. to 340° C. at 10° C./min, then cooled down to 10° C., and further heated up to 340° C. at 10° C./min, and a linear expansion coefficient was calculated from an amount of change in distortion of the sample per unit temperature range from 100° C. to 300° C. in the second heating-up.
  • TMA120C manufactured by Seiko Instruments Inc.
  • example size width of 3 mm, length of 10 mm; film thickness was measured and cross-sectional area of film was calculated
  • an amount of change in distortion of the film was measured when the temperature was heated up from 10° C. to 400° C. at 10° C./min with a load of 3 g.
  • a temperature at an inflection point of the amount of change was determined as a glass transition temperature.
  • Total-light transmittance was measured with the use of an integrating sphere-type hazemeter 300A (manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD.) in accordance with a method described in JIS K7105-1981.
  • Haze was measured with the use of the integrating sphere-type hazemeter 300A (manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD.) in accordance with a method described in JIS K7105-1981.
  • nx ⁇ ny is a maximum in-plane refractive index
  • ny is a minimum in-plane refractive index
  • nz is a refractive index in the thickness direction.
  • a polyamic acid solution was applied to a non-alkali glass having a size of 150 mm ⁇ 150 mm ⁇ 0.7 mm and was then dried in the air at 60° C. for 30 minutes. Then, the temperature was increased to 350° C. at a rate of 6.5° C./min under a nitrogen atmosphere, and drying was further carried out at 350° C. for 2 hours. Thus, a polyimide film was prepared. Note that a film thickness of the polyimide film was set to 10 ⁇ m. The polyimide film was observed in terms of detachment or floating from the glass.
  • CHDA trans-1,4-cyclohexanediamine
  • DMAC N,N-dimethylacetamide
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic anhydride
  • BPAF 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride
  • Ratios of respective added monomers were as follows: i.e., BPDA was 80 mol % and BPAF was 20 mol %, relative to 100 mol % of CHDA. Note that an amount of the diamine compound and the tetracarboxylic dianhydride added to the reaction solution was 20% by weight relative to the entire reaction solution. A weight-average molecular weight (Mw) of the obtained polyamic acid was 30,000.
  • the polyamic acid solution thus polymerized was applied to a glass plate with the use of a bar coater, and was then dried in the air at 60° C. for 30 minutes and in the nitrogen atmosphere at 350° C. for 1 hour.
  • a polyimide film having a film thickness of 10 ⁇ m was obtained.
  • a transmittance at a wavelength of 400 nm was 80%
  • (nx+ny)/2 ⁇ nz was 0.043
  • CTE was 33 ppm/K
  • a glass transition temperature was 367° C.
  • the result of evaluating the polyimide film is indicated in Table 2.
  • Example 1 80 20 100 30,000 DMAC 10
  • Example 2 60 40 100 32,000 DMAC 10
  • Example 3 50 50 100 40,000 DMAC 10
  • Example 4 80 20 100 45,000 DMAC 10
  • Example 5 50 50 100 45,000 DMAC 10
  • Example 6 99 1 100 50,000 DMAC 10
  • Example 7 97 3 100 50,000 DMAC 10
  • Example 8 95 5 100 50,000 DMAC 10 Com.
  • Ex. 1 100 100 45,000 DMAC 10 Com.
  • Ex. 2 100 100 45,000 NMP 10 Com.
  • Ex. 3 100 100 62,000 DMAC 10 Com.
  • Ratios of respective added monomers were as follows: i.e., BPDA was 60 mol % and BPAF was 40 mol %, relative to 100 mol % of CHDA. Note that an amount of the diamine compound and the tetracarboxylic dianhydride added to the reaction solution was 20% by weight relative to the entire reaction solution. A weight-average molecular weight (Mw) of the obtained polyamic acid was 32,000.
  • the polyamic acid solution thus polymerized was applied to a glass plate with the use of a bar coater, and was then dried in the air at 60° C. for 30 minutes and in the nitrogen atmosphere at 350° C. for 1 hour.
  • a polyimide film having a film thickness of 10 ⁇ m was obtained.
  • a transmittance at a wavelength of 400 nm was 82%
  • (nx+ny)/2 ⁇ nz was 0.018
  • CTE was 46 ppm/K
  • a glass transition temperature was 365° C.
  • the result of evaluating the polyimide film is indicated in Table 2.
  • Ratios of respective added monomers were as follows: i.e., BPDA was 50 mol % and BPAF was 50 mol %, relative to 100 mol % of CHDA. Note that an amount of the diamine compound and the tetracarboxylic dianhydride added to the reaction solution was 20% by weight relative to the entire reaction solution. A weight-average molecular weight (Mw) of the obtained polyamic acid was 40,000.
  • the polyamic acid solution thus polymerized was applied to a glass plate with the use of a bar coater, and was then dried in the air at 60° C. for 30 minutes and in the nitrogen atmosphere at 350° C. for 1 hour.
  • a polyimide film having a film thickness of 10 ⁇ m was obtained.
  • a transmittance at a wavelength of 400 nm was 82%
  • (nx+ny)/2 ⁇ nz was 0.011
  • CTE was 47 ppm/K
  • a glass transition temperature was 365° C.
  • the result of evaluating the polyimide film is indicated in Table 2.
  • Ratios of respective added monomers were as follows: i.e., BPDA was 80 mol % and BPAF was 20 mol %, relative to 100 mol % of CHDA. Note that an amount of the diamine compound and the tetracarboxylic dianhydride added to the reaction solution was 15% by weight relative to the entire reaction solution. A weight-average molecular weight (Mw) of the obtained polyamic acid was 45,000.
  • the polyamic acid solution thus polymerized was diluted with DMAC to a solid content concentration of 10%, and the solution thus diluted was applied to a glass plate with a bar coater, and was then dried in the air at 60° C. for 30 minutes and in the nitrogen atmosphere at 350° C. for 1 hour.
  • a polyimide film having a film thickness of 10 ⁇ m was obtained.
  • a transmittance at a wavelength of 400 nm was 78%
  • (nx+ny)/2 ⁇ nz was 0.073
  • CTE was 27 ppm/K
  • a glass transition temperature was 365° C.
  • the result of evaluating the polyimide film is indicated in Table 2.
  • Ratios of respective added monomers were as follows: i.e., BPDA was 50 mol % and BPAF was 50 mol %, relative to 100 mol % of CHDA. Note that an amount of the diamine compound and the tetracarboxylic dianhydride added to the reaction solution was 15% by weight relative to the entire reaction solution. A weight-average molecular weight (Mw) of the obtained polyamic acid was 45,000.
  • the polyamic acid solution thus polymerized was diluted with DMAC to a solid content concentration of 10%, and the solution thus diluted was applied to a glass plate with a bar coater, and was then dried in the air at 60° C. for 30 minutes and in the nitrogen atmosphere at 350° C. for 1 hour.
  • a polyimide film having a film thickness of 10 ⁇ m was obtained.
  • a transmittance at a wavelength of 400 nm was 79%
  • (nx+ny)/2 ⁇ nz was 0.044
  • CTE was 36 ppm/K
  • a glass transition temperature was 365° C.
  • the result of evaluating the polyimide film is indicated in Table 2.
  • Ratios of respective added monomers were as follows: i.e., BPDA was 99 mol % and BPAF was 1 mol %, relative to 100 mol % of CHDA. Note that an amount of the diamine compound and the tetracarboxylic dianhydride added to the reaction solution was 15% by weight relative to the entire reaction solution. A weight-average molecular weight (Mw) of the obtained polyamic acid was 50,000.
  • the polyamic acid solution thus polymerized was diluted with DMAC to a solid content concentration of 10%, and the solution thus diluted was applied to a glass plate with a bar coater, and was then dried in the air at 60° C. for 30 minutes and in the nitrogen atmosphere at 350° C. for 1 hour.
  • a polyimide film having a film thickness of 10 ⁇ m was obtained.
  • a transmittance at a wavelength of 400 nm was 74%
  • (nx+ny)/2 ⁇ nz was 0.120
  • CTE was 11 ppm/K
  • a glass transition temperature was 360° C.
  • a result of evaluation of adhesiveness to glass of a polyimide film, which had been obtained with the use of the polyamic acid solution diluted with DMAC to the solid content concentration of 10% was 3.
  • the result of evaluating the polyimide film is indicated in Table 2.
  • Ratios of respective added monomers were as follows: i.e., BPDA was 97 mol % and BPAF was 3 mol %, relative to 100 mol % of CHDA. Note that an amount of the diamine compound and the tetracarboxylic dianhydride added to the reaction solution was 15% by weight relative to the entire reaction solution. A weight-average molecular weight (Mw) of the obtained polyamic acid was 50,000.
  • the polyamic acid solution thus polymerized was diluted with by DMAC to a solid content concentration of 10%, and the solution thus diluted was applied to a glass plate with a bar coater, and was then dried in the air at 60° C. for 30 minutes and in the nitrogen atmosphere at 350° C. for 1 hour.
  • a polyimide film having a film thickness of 10 ⁇ m was obtained.
  • a transmittance at a wavelength of 400 nm was 77%
  • (nx+ny)/2 ⁇ nz was 0.120
  • CTE was 13 ppm/K
  • a glass transition temperature was 360° C.
  • the result of evaluating the polyimide film is indicated in Table 2.
  • Ratios of respective added monomers were as follows: i.e., BPDA was 95 mol % and BPAF was 5 mol %, relative to 100 mol % of CHDA. Note that an amount of the diamine compound and the tetracarboxylic dianhydride added to the reaction solution was 15% by weight relative to the entire reaction solution. A weight-average molecular weight (Mw) of the obtained polyamic acid was 50,000.
  • the polyamic acid solution thus polymerized was diluted with DMAC to a solid content concentration of 10%, and the solution thus diluted was applied to a glass plate with a bar coater, and was then dried in the air at 60° C. for 30 minutes and in the nitrogen atmosphere at 350° C. for 1 hour.
  • a polyimide film having a film thickness of 10 ⁇ m was obtained.
  • a transmittance at a wavelength of 400 nm was 78%
  • (nx+ny)/2 ⁇ nz was 0.115
  • CTE was 15 ppm/K
  • a glass transition temperature was 362° C.
  • the result of evaluating the polyimide film is indicated in Table 2.
  • the polyamic acid solution thus polymerized was applied to a glass plate with the use of a bar coater, and was then dried in the air at 60° C. for 30 minutes and in the nitrogen atmosphere at 350° C. for 1 hour.
  • a polyimide film having a film thickness of 10 ⁇ m was obtained.
  • a transmittance at a wavelength of 400 nm was 70%
  • (nx+ny)/2 ⁇ nz was 0.120
  • CTE was 11 ppm/K
  • a glass transition temperature was 360° C.
  • the result of evaluating the polyimide film is indicated in Table 2.
  • the polyamic acid solution thus polymerized was applied to a glass plate with the use of a bar coater, and was then dried in the air at 60° C. for 30 minutes and in the nitrogen atmosphere at 350° C. for 1 hour.
  • a polyimide film having a film thickness of 10 ⁇ m was obtained.
  • a transmittance at a wavelength of 400 nm was 49%
  • (nx+ny)/2 ⁇ nz was 0.160
  • CTE was 7 ppm/K
  • a glass transition temperature was 360° C.
  • the result of evaluating the polyimide film is indicated in Table 2.
  • the polyamic acid solution thus polymerized was applied to a glass plate with the use of a bar coater, and was then dried in the air at 60° C. for 30 minutes and in the nitrogen atmosphere at 350° C. for 1 hour.
  • a polyimide film having a film thickness of 10 ⁇ m was obtained.
  • a transmittance at a wavelength of 400 nm was 83%
  • (nx+ny)/2 ⁇ nz was 0.001
  • CTE was 52 ppm/K
  • a glass transition temperature was 376° C.
  • the result of evaluating the polyimide film is indicated in Table 2.
  • 4,4′-ODA 4,4′-diaminodiphenyl ether
  • the polyamic acid solution thus polymerized was applied to a glass plate with the use of a bar coater, and was then dried in the air at 60° C. for 30 minutes and in the nitrogen atmosphere at 350° C. for 1 hour.
  • a polyimide film having a film thickness of 10 ⁇ m was obtained.
  • a transmittance at a wavelength of 400 nm was 0%
  • (nx+ny)/2 ⁇ nz was 0.048
  • CTE was 41 ppm/K
  • a glass transition temperature was 375° C.
  • the result of evaluating the polyimide film is indicated in Table 2.
  • the polyamic acid solution thus polymerized was applied to a glass plate with the use of a bar coater, and was then dried in the air at 60° C. for 30 minutes and in the nitrogen atmosphere at 350° C. for 1 hour.
  • a polyimide film having a film thickness of 10 ⁇ m was obtained.
  • a transmittance at a wavelength of 400 nm was 0%
  • (nx+ny)/2 ⁇ nz was 0.060
  • CTE was 36 ppm/K
  • a glass transition temperature was 357° C.
  • the result of evaluating the polyimide film is indicated in Table 2.
  • the polyimides of Examples 1 through 8 achieve (i) higher transparency, i.e., the transmittance over 70% at a wavelength of 400 nm, (ii) better evaluation of adhesiveness to glass, i.e., 3 or more, and (iii) lower birefringence, i.e., (nx+ny)/2 ⁇ nz ⁇ 0.120, as compared with the polyimides of Comparative Examples 1, 2, 4, and 5. Moreover, the polyimides of Examples 1 through 8 achieve lower thermal expansion coefficient, i.e., 50 ppm/K or lower, as compared with the polyimide of Comparative Example 3.
  • the polyimide or a polyimide prepared by the use of the polyamic acid (i) has low birefringence in addition to heat resistance, low thermal expansion property, and transparency and (ii) provides good adhesiveness between the support and the polyimide. Therefore, each of the polyamic acid, the polyimide, and the polyamic acid solution of the present invention is expected to be used in a field and a product for which these characteristics are effective.
  • Examples of such a field and a product encompass a printed matter, a color filter, a flexible display, an optical film, a liquid crystal display device, an image display device such as an organic EL and an electronic paper, a 3-D display, a touch panel, a transparent conductive film substrate, and a solar cell.
  • a printed matter a color filter, a flexible display, an optical film, a liquid crystal display device, an image display device such as an organic EL and an electronic paper, a 3-D display, a touch panel, a transparent conductive film substrate, and a solar cell.
  • Each of the polyamic acid, the polyimide, and the polyamic acid solution of the present invention is further expected to be used for an alternative material for a part which has conventionally been made of glass.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
US14/409,126 2012-07-02 2013-06-25 Polyamic acid, polyimide, polyamic acid solution, and use of polyimide Expired - Fee Related US9353223B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2012-148588 2012-07-02
JP2012148588 2012-07-02
PCT/JP2013/067370 WO2014007112A1 (ja) 2012-07-02 2013-06-25 ポリアミド酸、ポリイミド、ポリアミド酸溶液、およびポリイミドの利用

Publications (2)

Publication Number Publication Date
US20150183931A1 US20150183931A1 (en) 2015-07-02
US9353223B2 true US9353223B2 (en) 2016-05-31

Family

ID=49881869

Family Applications (1)

Application Number Title Priority Date Filing Date
US14/409,126 Expired - Fee Related US9353223B2 (en) 2012-07-02 2013-06-25 Polyamic acid, polyimide, polyamic acid solution, and use of polyimide

Country Status (6)

Country Link
US (1) US9353223B2 (ja)
JP (1) JP5695276B2 (ja)
KR (1) KR102009067B1 (ja)
CN (1) CN104395376B (ja)
TW (1) TWI549991B (ja)
WO (1) WO2014007112A1 (ja)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9828469B2 (en) 2013-09-27 2017-11-28 Toray Industries, Inc. Polyimide precursor, polyimide resin film produced from said polyimide precursor, display element, optical element, light-receiving element, touch panel and circuit board each equipped with said polyimide resin film, organic EL display, and methods respectively for producing organic EL element and color filter
KR102367682B1 (ko) * 2014-03-12 2022-02-25 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 표시장치 및 그 제조방법, 및 표시 장치용 폴리이미드 필름
WO2016136597A1 (ja) * 2015-02-24 2016-09-01 株式会社カネカ ポリイミド積層体の製造方法およびその利用
CN108137931B (zh) * 2015-10-16 2021-06-08 住友化学株式会社 树脂溶液组合物
JP7248394B2 (ja) * 2017-09-29 2023-03-29 日鉄ケミカル＆マテリアル株式会社 ポリイミドフィルム及び金属張積層体
KR102350095B1 (ko) 2018-01-03 2022-01-11 주식회사 엘지화학 방향족 폴리(아미드-이미드) 공중합체 필름과 이의 제조 방법
CN112004858B (zh) 2018-03-30 2023-06-30 株式会社钟化 聚酰胺酸、聚酰胺酸溶液、聚酰亚胺、聚酰亚胺膜、层叠体及柔性装置、以及聚酰亚胺膜的制造方法
US11945911B2 (en) 2018-06-22 2024-04-02 Mitsui Chemicals, Inc. Polyamic acid, varnish containing same, film, touch panel display, liquid crystal display, and organic EL display
CN112384571A (zh) 2018-06-22 2021-02-19 三菱化学株式会社 含有沸石的聚酰亚胺树脂复合材、含有沸石的聚酰亚胺树脂前驱体组合物、膜和电子装置
JP7412094B2 (ja) 2018-06-28 2024-01-12 旭化成株式会社 ポリイミド前駆体樹脂組成物
KR102551047B1 (ko) * 2019-02-01 2023-07-04 주식회사 엘지화학 폴리이미드 필름, 이를 이용한 플렉서블 기판 및 플렉서블 기판을 포함하는 플렉서블 디스플레이
JP2024503967A (ja) * 2021-12-08 2024-01-30 エルジー・ケム・リミテッド ポリイミド系樹脂フィルムおよびこれを用いたディスプレイ装置用基板、および光学装置
KR20240023948A (ko) 2022-08-16 2024-02-23 에스케이이노베이션 주식회사 폴리이미드 조성물, 플렉시블 스마트 윈도우 및 플렉시블 스마트 윈도우의 제조 방법

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002161136A (ja) 2000-09-14 2002-06-04 Sony Chem Corp ポリイミド前駆体、その製造方法及び感光性樹脂組成物
JP2005306983A (ja) 2004-04-21 2005-11-04 Fuji Photo Film Co Ltd 光学フィルムおよび画像表示装置
JP2006206825A (ja) 2005-01-31 2006-08-10 Jfe Chemical Corp 芳香族ポリイミド樹脂前駆体及び芳香族ポリイミド樹脂
JP2007091701A (ja) 2005-08-31 2007-04-12 Jfe Chemical Corp フルオレニル基およびエステル基を含有するテトラカルボン酸類、フルオレニル基含有ポリエステルイミド前駆体、およびフルオレニル基含有ポリエステルイミド、ならびにこれらの製造方法
US20090088551A1 (en) 2007-09-27 2009-04-02 E. I. Du Pont De Nemours And Company Polyimide film
TW201012851A (en) 2008-09-29 2010-04-01 Sony Chem & Inf Device Corp Printed wiring board and method for manufacturing same
JP2010235641A (ja) 2009-03-30 2010-10-21 Sony Chemical & Information Device Corp ポリアミック酸溶液、ポリイミド及び光学装置
WO2012011590A1 (ja) 2010-07-22 2012-01-26 宇部興産株式会社 ポリイミド前駆体、ポリイミドおよびその製造に使用される材料
JP2012041530A (ja) 2010-07-22 2012-03-01 Ube Industries Ltd 共重合ポリイミド前駆体及び共重合ポリイミド

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002161136A (ja) 2000-09-14 2002-06-04 Sony Chem Corp ポリイミド前駆体、その製造方法及び感光性樹脂組成物
JP2005306983A (ja) 2004-04-21 2005-11-04 Fuji Photo Film Co Ltd 光学フィルムおよび画像表示装置
JP2006206825A (ja) 2005-01-31 2006-08-10 Jfe Chemical Corp 芳香族ポリイミド樹脂前駆体及び芳香族ポリイミド樹脂
JP2007091701A (ja) 2005-08-31 2007-04-12 Jfe Chemical Corp フルオレニル基およびエステル基を含有するテトラカルボン酸類、フルオレニル基含有ポリエステルイミド前駆体、およびフルオレニル基含有ポリエステルイミド、ならびにこれらの製造方法
US20090088551A1 (en) 2007-09-27 2009-04-02 E. I. Du Pont De Nemours And Company Polyimide film
JP2009079165A (ja) 2007-09-27 2009-04-16 Du Pont Toray Co Ltd ポリイミドフィルム
TW201012851A (en) 2008-09-29 2010-04-01 Sony Chem & Inf Device Corp Printed wiring board and method for manufacturing same
JP2010080878A (ja) 2008-09-29 2010-04-08 Sony Chemical & Information Device Corp プリント配線板およびその製造方法
JP2010235641A (ja) 2009-03-30 2010-10-21 Sony Chemical & Information Device Corp ポリアミック酸溶液、ポリイミド及び光学装置
WO2012011590A1 (ja) 2010-07-22 2012-01-26 宇部興産株式会社 ポリイミド前駆体、ポリイミドおよびその製造に使用される材料
JP2012041530A (ja) 2010-07-22 2012-03-01 Ube Industries Ltd 共重合ポリイミド前駆体及び共重合ポリイミド
US20130178597A1 (en) 2010-07-22 2013-07-11 Ube Industries, Ltd. Polyimide precursor, polyimide, and materials to be used in producing same

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
English Translation of First Office Action, Taiwanese Application No. 102123045, dated Nov. 5, 2015 (9 pages).
International Preliminary Report on Patentability, PCT/JP2013/067370, Jan. 15, 2015.
International Search Report, PCT/JP2013/067370, Oct. 1, 2013.

Also Published As

Publication number Publication date
TW201410738A (zh) 2014-03-16
JPWO2014007112A1 (ja) 2016-06-02
JP5695276B2 (ja) 2015-04-01
KR102009067B1 (ko) 2019-08-08
WO2014007112A1 (ja) 2014-01-09
CN104395376B (zh) 2016-09-14
TWI549991B (zh) 2016-09-21
KR20150031434A (ko) 2015-03-24
US20150183931A1 (en) 2015-07-02
CN104395376A (zh) 2015-03-04

Similar Documents

Publication Publication Date Title
US9353223B2 (en) Polyamic acid, polyimide, polyamic acid solution, and use of polyimide
US9777137B2 (en) Polyamic acid, polyimide, polyamic acid solution, polyimide solution, polyimide films obtained from these solutions, and use of polyimide films
JP7122437B2 (ja) ポリイミド、ポリイミド積層体及びフレキシブルデバイス基板
US10745519B2 (en) Polyimide resin, polyimide solution, film, and method for producing same
US11059742B2 (en) Thermally stable, flexible substrates for electronic devices
US20210024699A1 (en) Polyamic acid, polyamic acid solution, polyimide, polyimide film, laminate and flexible device, and method for producing polyimide film
US20180037698A1 (en) Polyimide precursor resin composition
US20140072813A1 (en) Polyamide-imide solution and polyamide-imide film
US11274182B2 (en) Poly(amic acid), poly(amic acid) solution, polyimide, polyimide film, layered product, flexible device, and production method for polyimide film
US20210009760A1 (en) Polyamic acid and method for producing same, polyamic acid solution, polyimide, polyimide film, laminate and method for producing same, and flexible device and method for producing same
JPWO2018042999A1 (ja) ポリアミド酸、ポリアミド酸溶液、ポリイミド、ポリイミド膜、積層体およびフレキシブルデバイス、ならびにポリイミド膜の製造方法
JP6687442B2 (ja) ポリアミド酸、ポリイミド、ポリアミド酸溶液、およびポリイミドの利用
WO2017159538A1 (ja) ポリアミド酸、ポリアミド酸溶液、ポリイミド、およびポリイミド基板ならびにそれらの製造方法
CN113604042A (zh) 聚酰亚胺基膜及包括该聚酰亚胺基膜的柔性显示面板
JP7349253B2 (ja) ポリアミド酸、ポリアミド酸溶液、ポリイミド、ポリイミド膜、積層体およびフレキシブルデバイス、ならびにポリイミド膜の製造方法。
US20240199878A1 (en) Resin composition, formed article and film
JP2019172746A (ja) ポリアミド酸、ポリアミド酸溶液、ポリイミド、ポリイミド膜、積層体およびフレキシブルデバイス、ならびにポリイミド膜の製造方法。
TWI847056B (zh) 聚醯亞胺膜
CN114854196B (zh) 聚酰亚胺膜
WO2023132310A1 (ja) 樹脂組成物、成形体およびフィルム
US20220135470A1 (en) Polyamideimide Film and Window Cover Film Including the Same
CN117264252A (zh) 一种结合抗氧剂的高温耐黄变无色透明聚酰亚胺薄膜的制备方法
CN112280068A (zh) 聚酰胺酰亚胺膜

Legal Events

Date Code Title Description
AS Assignment

Owner name: KANEKA CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FUJII, MARI;OZAWA, SHINJI;ABO, TOMOHIRO;REEL/FRAME:034546/0310

Effective date: 20141118

ZAAA Notice of allowance and fees due

Free format text: ORIGINAL CODE: NOA

ZAAB Notice of allowance mailed

Free format text: ORIGINAL CODE: MN/=.

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362